Detergent composition



Patented May 25, 1943 DETERGENT COMPOSITION Varton Mardiras Kalusdian,New York, N. Y., as-

signor to The Mathieson Alkali Works, Inc., New York, N. Y., a.corporation of Virginia No Drawing. Application March 24, 1938, SerialNo. 197,867

16 Claims.

Thi invention relates to improved detergent compositions, and moreparticularly to substantially dry stable salt mixtures having improvedcharacteristics which are useful as detergents. The invention alsoincludes the aqueous solutions formed by dissolving the compositions ofthe invention in water.

The new and improved compositions of the present invention are saltmixtures containing a solid calcium hypochlorite of high purity, sodiumcarbonate, and a synthetic organic detergent salt hereinafter more fullydescribed. An acid salt such as, for example, sodium bicarbonate mayadvantageously be incorporated in this mixture if it is desired toreduce the alkalinity when a large proportion of sodium carbonate ispresent in the mixture. The product of my invention provides a drystable detergent mixture readily soluble in water which is of specialvalue in cleaning operations, for example, in rug cleaning where strongdetergent and wetting action is required while at the same time anychemical action with the material being cleaned must be avoided. Themixture of the present invention also possesses valuable disinfectingand germicidal properties.

It has previously been proposed to employ mix- 1 tures of a stablecalcium hypochlorite and soda ash as a cleansing and Wagent. The drystable mixture of e present invention possesses important advantagesover such a mixture, particularly in operations where soap wouldnormally be employed either preceding or following the use of such ahypochlorite-soda ash mixture. As an example of an application of themixture of my invention under these conditions may be mentionedoperations such as rug cleaning wherein the present salt mixturespossess important advantages such as increased wetting power as well ashigh detergency. The use and advantage upwards of 60%. The free limecontent is preferably maintained at a low value. The calciumhypochlorite referred to herein as useful in my product is not to beconfused with the conventional bleaching powder or chlorinated lime fromwhich it differs materially, both as to chemical constitution and in itsexceptionally high content of available chlorine. As examples storage ofhypochlorite compositions containing of calcium hypochlorite productssuitable for use in the composition of the present invention may bementioned the products whose preparation is described in United StatesPatents Nos. 1,481,039, 1,481,040, 1,713,650, 1,713,654, 1,713,668 and1,713,669. The term calcium hypochlorite as used herein refers to aproduct having the properties just described. The high stability whichsuch a hypochlorite product possesses is particu larly advantageous inthe mixed product of the present invention since it permits storage forconsiderable periods of time without decomposition. Its stability is duein part to its low content of calcium chloride, which at most should notexceed about 10% of the hypochlorite product and preferably should notexceed 2%3%. When this salt which is very hygroscopic is present insubstantial amount, it not only makes the product diflicult to keep dry,but it also decreases the stability of the product due to the hydrolysisoccasioned by the absorbed water.

The materials above referred to broadly as synthetic organic detergentsalts may include a wide variety of organic compounds having strongdetergent and wetting action. The organic or non-polar groups of thesedetergent compounds include a wide variety of organic groups. Inaddition to carbon, hydrogen and oxygen, these groups may contain sulfuror nitrogen, or other elements commonly associated with them in organiccompounds. Such groups include saturated, or unsaturated hydrocarbons,ethers, thioethers, primary and secondary alcohols, thioalcohols,ketones, thioketones, and esters. These groups may furthermore containaromatic or heterocyclic ring structures. The polar groups contained inthe detergents used in my invention are more limited in number. They arein most cases r 1 f sulfur or phosphorous; the sulfur containing acidgroups occurring usually as sulfate or sulfonate.

The cations which form the salts with the acid groups in these compoundsinclude the alkali metals, the alkaline earth metals and the am-" moniuminn. 'T, e ammonium ion may also constitute the salt forming ion as, forexample, in

a quaternary ammonium salt. The non-polar groups mentioned above usuallyform anions in solution, but the non-polar groups in quaternary ammoniumcompounds form cations in solutions. Salts of sulfated higher alcoholsare generally useful as detergents in the herein described mixtures. Anexample of another class of satisfactory detergent compounds are thesalts of sulfonated long chain compounds. These are distinguished fromthe referred to sulfates by the fact that the sulfonic group is attacheddirectly to a hydrocarbon group, whereas the alcohol sulfates are inreality sulfuric acid esters of the alcohols. Specific examples ofsynthetic organic detergent salts useful in the composition of myinvention are as ogiumlamidsulfate, sodium laur l W W 5 51mm ethylenemethyl la uramide sulfonate, and p l l amm nium chl de.

' Soaps react alkaline in water solution and form insoluble compoundswith the alkaline earth metals. Under the same conditions the watersoluble detergents of the present invention do not form such insolublecompounds. They produce substantially neutral aqueous solutions,apparently owing to the fact that their solubilizing groups are morestrongly acidic than the carboxyl group in soap with the result thattheir metallic salts are more nearly neutral. These detergent compoundstherefore do not contain the carboxyl group as such, but may contain itin a muzzled form, for example as an ester grouping. By the phrasesynthetic organic detergent salt as used in this application and in theclaims, I refer to a detergent compound of the above referred to type,and I intend to exclude organic compounds which may be classified assoaps which give a strong alkaline reaction in aqueous solution andwhich precipitate insoluble compounds with the alkaline earth metals.

I have found that a calcium hypochlorite having the above-describedstable properties may be mixed with Web and a synthetic organicdetergent salt 0 e class described above to produce a dry mixture havinghigh stability and improved properties. A stable hypochloritecomposition is thus provided which does not lose its available chlorineon standing, and in which the stability of the organic detergentcomponent is not impaired. It will be apparent that the organicdetergent salt and the other components of the mixture should besubstantially dry before being intimately admixed with the calciumhypochlorite by any means suitable for comminuting and admixing solidchemical substances.

The relative proportions in which the various components are present inthe salt mixtures of the present invention may vary over wide limits. Inpractical operation the desirable content of the mixture ispredetermined and the mixture dissolved in water in an amountpredetermined to be necessary to effect the desired degree of detergencyand other valuable functions. When the mixture is dissolved in water ina suitable container the calcium of the hypochlorite is precipitated asinsoluble calcium carbonate. The clear solution may then be decanted andsupplied to the cleaning operation. Since an amount of carbonateequivalent to the calcium ion present is removed from the solution, theamount of soda ash present in the original mixture should be in excessof an amount equivalent to the calcium hypochlorite present. In this wayan excess of soda ash will remain in the solution imparting theretovaluable detergent qualities. In many cases it is desirable to have thesolutions used in a lower pH range. The pH value which would be impartedto the solution by the excess sodium carbonate may be lowered byincorporating in the dry mixture at predetermined proportion of sodiumbicarbonate. In addition to the variation permitted in the new saltmixtures of this invention between the proportion sodium carbonate,sodium bicarbonate when present, and calcium hypochlorite with respectto each other, there is considerable latitude permissible in theproportion of the organic detergent salt with respect to the totalquantity of the above-mentioned inorganic salts present. The relativeamount of organic detergent incorporated in the mixture is governed bythe amount of detergent and wetting action desired in the specificoperation for which the mixture is to be employed. In general I havefound that dry mixtures containing between 2 and 3 parts by weight ofthe above-referred to inorganic salt mixture and one part by weight ofthe organic detergent salt mixture, are satisfactory. Such mixturesrepresent a proportion of organic detergent in the total dry mixture offrom 25-33%. Tests which I have conducted indicate that solutions ofsalt mixtures when the components are within these concentration limitsclosely approach a maximum penetrating or wetting ability. It is to beunderstood, however, that a greater or less proportion of detergent saltthan the amount just mentioned may sometimes be preferred.

I have found that the new salt mixtures of the present invention areparticularly useful in the art of rug cleaning. The use of such mixturesmakes possible an efficient and simple one step process for the cleaningof rugs, carpets and other fabrics. In the past rugs have customarilybeen subjected to a shampooing preceded by beat ing and vacuumtreatments and followed by cumbersome rinsing and drying steps. One ofthe greatest difficulties encountered was the loosening and completeremoval of the adhesive dirt held at the base of the pile by soot andother greasy materials which collects in such a fabric with constantuse. Complete removal was seldom accomplished in actual rug cleaningpractice. A further major difficulty was the complete elimination ofsoap solution from the rug, and particularly from the base of the pileafter shampooing. In spite of copious rinsing, satisfactory removal wasseldom accomplished. As a result of this failure to completely removethe soap it remained as a coating on the fibers thus increasing thetendency of dust particles to adhere to the fiber in such a way thatordinary cleaning methods, including the use of vacuum cleaners, failedto remove such dirt. In addition, the soap residue frequently becamerancid thus preventing the pile from regaining its fresh springyappearance. Such difiiculties are overcome and many independentimprovements attained by the use of the salt mixtures of this inventionin such a cleaning process. The increased solubility of the mixturefacilitates the removal of the reagents from the fabric thus eliminatingextensive rinsing operations. The loss of substantial proportions ofcleansing agent accompanied by the precipitation of insoluble soaps whenhard waters are used is avoided. The increased wetting and penetratingaction of solutions prepared from the mixtures of the present inventionresult in increased efliciency of soil removal and time of reaction ascompared to the results obtained by the use of soaps. In the case offabrics having a "sheen finish, the original sheen is restored. Thecolors of the fabric are freshened and the designs clarifled. Stains areremoved and the fabric is efflciently deodorized and disinfected.

The following will serve as illustrative examples of the use of themixture of my invention in two specific instances of rug cleaning. Inthese examples the dry salt mixture used had the following approximatecomposition: 16% calcium hypochlorite; 26% sodium carbonate; 26% sodiumbicarbonate; and 30% of a mixture consisting es- Eentially of sod iumlaur yl sulfate with small proportions of sodium'myristyfsulfate andsodium palmityl sulfate. 2 lbs. of the dry salt mixture were dissolvedin 50 gallons of water at approximately 72 F. The solution wasthoroughly stirred and the precipitated calcium carbonate allowed tosettle. The clear solution was fed by gravity into the center of amechanical rotary brush with which the rug which was spread on the doorwas scrubbed. The rug is usually cleaned on both sides in the samemanner; in most cases the back of the rug being cleaned first. By thisexpedient the greasy and wax-like materials at the base of the pile arehydrolyzed thus freeing the dirt particles so that they arereadilyemulsifled and brought to the surface when subjected to thesubsequent cleaning on the right side. The cleaning of a 9 x 12 rugshould take approximately 3 minutes on each side by such a procedure.

An alternative procedure to the just described "floor method ofoperation involves the .use of an automatic feeder machine. The rug tobe cleaned was fed into a device having arranged therein flat brusheswhich vibrated alternately in a direction parallel to the direction oftravel of the rug. An aqueous solution containing from 1 lbs. to 2 lbs.of the detergent salt mixture of the present invention per 50 gallons ofwater at a temperature up to 100 F. was applied to the rug or carpetjust prior to its contact with the horizontally vibrating brushes. Aftertreatment on one side the rug was turned and the reverse side treated inthe same manner. The fabric was rinsed and wrung in a subsequent stageof its passage thru the machine.

It is to be understood that while the new and improved dry stable saltmixture of the present invention is particularly useful in the cleaningof rugs, its use is not restricted to this purpose, but mayadvantageously be applied to operations where simultaneous detergent andgermicidal or bleaching action is desired.

I claim:

1. A substantially dry stable salt mixture comprising a stable calciumhypochlorite, sodium carbonate in an amount in excess of that necessaryto react with all of the calcium present in the mixture, and a syntheticorganic water soluble detergent salt which does not produce an insolubleprecipitate in the presence of calcium ions.

2. A substantially dry stable salt mixture comprising a stable calciumhypochlorite containing upwards of 50% available chlorine andsubstantially free of calcium chloride, sodium carbonate in an amount inexcess of that necessary to react with all of the calcium present in themixture, and a synthetic organic water soluble detergent salt which doesnot produce an insoluble precipitate in the presence of calcium ions.

3. A substantially dry stable salt mixture comprising a stable calciumhypochlorite, sodium carbonate in an amount in excess of that necessaryto react with all of the calcium present in the mixture, sodiumbicarbonate and a synthetic organic water soluble detergent saltwhichdoes not produce an insoluble precipitate in the presence ofcalcium ions.

4. A substantially dry stable salt mixture comprising a stable calciumhypochlorite containing upwards of 50% available chlorine andsubstantially free of calcium chloride, sodium carbonate in an amount inexcess of that necessary to react with all of the calcium present in themixture, sodium bicarbonate, and a synthetic organic water solubledetergent salt which does not produce an insoluble precipitate in thepresence of calcium ions.

5. A substantially dry stable salt mixture comprising a stable calciumhypochlorite containing upwards of 50% available chlorine andsubstantially free of calcium chloride, sodium carbonate in an amount inexcess of that necessary to react with all of the calcium present in themixture, sodium bicarbonate, and a water soluble detergent sulfate saltof a higher alcohol which does not produce an insoluble precipitate inthe presence of calcium ions and which is selected from the classconsisting of the alkali metal alcohol sulfates, the alkaline earthmetal alcohol sulfates and ammonium alcohol sulfates.

6. A substantially dry stable salt mixture comprising a stable calciumhypochlorite containing upwards of 50% available chlorine andsubstantially free of calcium chloride, sodium carbonate in an amount inexcess of that necessary to react with all of the calcium present in themixture, sodium bicarbonate, and a detergent sodium salt of a higheralcohol sulfate which does not produce an insoluble precipitate in thepresence of calcium ions.

'7. A substantially dry stable salt mixture comprising a stable calciumhypochlorite containing upwards of 50% available chlorine andsubstantially free of calcium chloride, sodium carbonate in an amount inexcess of that necessary to react with all of the calcium present in themix- ;uzg. sodium bicarbonate, and sodium lauryl sul- 8. A substantiallydry stable salt mixture comprising a stable calcium hypochloritecontaining upwards of 50% available chlorine and substantially free ofcalcium chloride, sodium carbonate in an amount in excess of thatnecessary to react with all of the calcium present in the mixture.sodium bicarbonate, and a water soluble salt of a sulfonated organiccompound of high molecular weight having detergent properties which doesnot produce an insoluble precipitate in the presence of calcium ions.

9. A substantially dry stable salt mixture comprising a stable calciumhypochlorite containing upwards of 50% available chlorine andsubstantially free of calcium chloride, sodium carbonate in an amount inexcess of that necessary to react with all of the calcium present in themixture, sodium bicarbonate, and sodium ethylene palmitate sulfonate.

10. A substantially dry stable salt mixture comprising a stable calciumhypochlorite containing upwards of 50% available chlorine andsubstantially free of calcium chloride, sodium carbonate in an amount inexcess of that necessary to react with all of the calcium present in themixture, sodium bicarbonate and sodium ethylene methyl lauramidesulfonate.

11. A substantially dry stable salt mixture comprising a stable calciumhypochlorite containing upwards of 50% available chlorine andsubstantially free of calcium chloride, sodium carbonate in an amount inexcess of that necessary to react with all of the calcium present in themixture, sodium bicarbonate and a water soluble quaternary ammonium salthaving detergent properties and containing at least one high molecularweight organic group as a substituent.

12. An aqueous solution formed by dissolving in water a stable calciumhypochlorite, sodium carbonate in excess of that necessary to react withall of the calcium present and. a synthetic organic water solubledetergent salt which does not produce an insoluble precipitate in thepresence of calcium ions.

13. An aqueous solution formed by dissolving in water a stable calciumhypochlorite, sodium carbonate in excess of that necessary to react withall of the calcium present, sodium bicarbonate, and a synthetic organicwater soluble detergent salt which does not produce an insolubleprecipitate in the presence of calcium ions.

14. A substantially dry stable salt mixture comprising a stable calciumhypochlorite, sodium carbonate in an amount in excess of that necessaryto react with all of the calcium present in the mixture, and a syntheticorganic water soluble detergent salt which does not produce an insolubleprecipitate in the presence of calcium ions, said salts being presentinthe ratio of 1 part by weight of the organic detergent salt to about 2to 3 parts by weight of the inorganic salts.

15. A substantially dry stable salt mixture comprising a stable calciumhypochlorlte, sodium carbonate in an amount in excess of that necessaryto react with all of the calcium present in the mixture, sodiumbicarbonate, and a synthetic organic water soluble detergent salt whichdoes not produce an insoluble precipitate in the present of calciumions, said salts being present in the ratio of 1 part by weight of theorganic detergent salt to about 2 to 3 parts by weight of the inorganicsalts.

16. A substantially dry stable salt mixture comprising a stable calciumhypochlorite, sodium carbonate in an amount in excess of that necessaryto react with all of the calcium present in the mixture, sodiumbicarbonate, and sodium lauryl sulfate, said salts being present in theratio of 1 part by weight of sodium lauryl sulfate to about 2 to 3 partsby weight of the inorganic salts.

VARTON MARDIRAS KALUSDIAN.

